DE602005003113T2 - COATING WITH A POLYMER LAYER USING A PULSED PLASMA LOW POWER IN A LARGE VOLUME PLASMA CHAMBER - Google Patents

Abstract

A method for depositing a polymeric material onto a substrate, said method comprising introducing an organic monomeric material in a gaseous state into a plasma deposition chamber, igniting a glow discharge within said chamber, and applying a high frequency voltage as a pulsed field, at a power of from 0.001 to 500 w/m3 for a sufficient period of time to allow a polymeric layer to form on the surface of the substrate. The method is particularly suitable for producing oil and water repellent coatings, in particular where the monomeric material contains haloalkyl compounds. Apparatus particularly adapted to carry out the method of the invention is also described and claimed.

Description

The The present invention relates to the coating of surfaces, in particular on the production of oil and water-repellent surfaces as well as coated articles obtained therefrom.

Oil and water repellent Treatments for a big Variety of surfaces are in widespread use. For example, it may be desirable be, solid surfaces, such as metal, glass, ceramics, paper, polymers, etc., such surfaces to improve their durability properties or Prevent pollution.

Special Substrates requiring such coatings are textile Substances, in particular for the application for Outdoor clothing, sportswear, casual wear and for military applications. The treatments generally require the incorporation of a fluoropolymer in the garment or, more particularly, the binding of a fluoropolymer on the surface of the clothing material. The degree of oil repellency and water repellency is a function of the number and length of the Fluorocarbon groups or fluorocarbon residues in the available space can be fitted. The bigger the Concentration of such radicals is, the greater the repellency of the Finishes.

In addition, however, the polymeric compounds must also be capable of forming permanent bonds with the substrate. Oil and water repellent fabric treatments generally rely on fluoropolymers applied to the fabric in the form of an aqueous emulsion. The fabric remains breathable and permeable to air as the treatment merely results in a coating of the fibers with a very thin, liquid-repellent film. In order to preserve these types of finish, they are sometimes used in conjunction with crosslinking resins which bind the fluoropolymer treatment material to the fibers. While high levels of wash resistance and dry cleaning resistance can be achieved in this manner, the crosslinking resins can significantly damage cellulosic fibers and reduce the mechanical strength of the material. Chemical processes for the production of oil and water repellent textiles are disclosed, for example, in WO 97/13024 and the British Patent 1,102,903 or in Lewin et al., Handbook of Fiber Science and Technology, Marcel and Dekker Inc., New York, (1984), Volume 2, Part B, Chapter 2.

to Deposition of polymeric coatings on a range of surfaces were Plasma deposition method used to a very large extent. These Technology is recognized as a clean, dry technique, in comparison with conventional wet chemical process produces little waste. In the application This process produces plasmas from organic molecules which are subjected to an electric field. If this is in the presence of a substrate, the radicals and molecules of the compound polymerize in the plasma in the gas phase and react to grow a polymer film on the substrate. In the conventional Polymer synthesis tends to produce structures, The recurring units contain a strong similarity possess with the monomer species while one using a Plasma-generated polymer network can be extremely complex.

WO 98/58117 describes the production of oil or water repellent coatings on a surface using monomeric unsaturated organic compounds, and in particular unsaturated halocarbon compounds polymerized on the surface using a plasma deposition process. This process gives coatings with good oil and water repellency, this being illustrated using small units of 470 cm ³ .

WO 03/090939 discloses a similar plasma coating process performed in a chamber of 0.3 m ³ .

For the most Commercial applications are much larger sized production units required. initial However, experiments showed that the transmission of small-sized units applied conditions to larger chambers gave no satisfactory results.

According to the present invention, there is provided a method of depositing a polymeric material on a substrate, the method comprising:
Introducing a monomeric material in a gaseous state into a plasma deposition chamber in which a plasma zone has a volume of at least 0.5 m ³ , igniting a glow discharge inside the chamber, and applying a voltage in the form of a pulsed field at a power of 0.001 to 500 watts / m ³ for a period of time sufficient to form a polymer layer on the surface of the substrate enough.

Of the Expression "in one gaseous State, "as he used herein refers to gases or vapors, either alone or in admixture, as well as on aerosols.

These conditions are particularly suitable for the deposition of high quality oil and water repellent surfaces of uniform thickness in large chambers in which the plasma zone has a volume of 0.5 m ³ or more, about 0.5-10 m ³ , and desirably about 1 m ³ has. The layers produced in this manner have good mechanical strength and remain essentially in place in a conventional washing process.

The power levels, and in particular the power densities, which give the best results are lower than those conventionally used in this type of process. This is totally unexpected. Specifically, a power of 0.001 to 100 W / m ^3, and desirably 0.01 to 10 W / m ^{3 is} used.

The Dimensions of the chamber are chosen so that the special treated Substrate finds room in it; in general, the dimensions are of more reasonable Size, so they can accommodate plasma zones with the volumes described above. So should, for example, cuboid Chambers generally for be suitable for a wide range of applications; it can, however if necessary also elongated or rectangular chambers are constructed, for example, if the substrates generally have this profile, such as wood, fabric rolls, etc. flat materials can be processed using a roll-to-roll arrangement.

The Chamber can be a tight sealable container be used to perform batch processes, or he may be inlets and outlets for substrates for him to use in a continuous process can be. In the latter case in particular, they are used for production a plasma discharge within the chamber required pressure conditions maintained using high volume flow pumps, as usual for example, in a device with a "gas leak" ("whistling leak ") state of the Technology is.

The monomer material is in particular a material, as it is known in WO 98/58117 is described. It is specifically an organic compound having a chain of carbon atoms, at least some of which are preferably substituted with halogen.

The In particular, compounds are unsaturated and thus contain at least a double bond or triple bond capable of forming a react polymeric compound. The compounds preferably contain at least one double bond.

By "chain" is meant the carbon atoms form straight or branched chains. The chains are cheap non-cyclic. Those used in the process of the invention Compounds have at least one such chain. suitable Chains have 3 to 20 carbon atoms and even cheaper 6 to 12 carbon atoms.

In Monomer compounds used in the process may be a double bond or contain a triple bond within a chain and so on Alkene or represent an alkyne. Alternatively, the compounds may have a Have alkyl chain, optionally with halogen as a substituent substituted, either directly or via a functional group, such as an ester or sulfonamide group, on an unsaturated one Unit is attached.

Of the Term "halogen" as used herein Meaning refers to fluorine, chlorine, bromine and iodine. Preferred halogen substituents are fluorine substituents. The term "aryl" refers to aromatic cyclic groups such as phenyl or naphthyl, especially phenyl. The term "alkyl" refers to straight or branched chains of carbon atoms, desirably of a length of up to 20 carbon atoms. The term "alkenyl" refers to straight-chain or straight chain branched unsaturated Chains that are favorably Have 2 to 20 carbon atoms.

Monomer compounds in which the chains have unsubstituted alkyl or alkenyl groups are useful for preparing coatings that are water repellent. By replacing at least some of the hydrogen atoms in these chains by at least some halogen atoms, the coating can also be made oil repellent.

In In a preferred aspect, the monomer compounds thus contain Haloalkyl units or they are haloalkenyl compounds. Therefore contains the plasma used in the process of the invention preferably a monomeric unsaturated organic compound containing haloalkyl groups.

worin bedeuten:
R¹, R² und R³ unabhängig voneinander einen Substituenten, der ausgewählt ist unter Wasserstoff, Alkyl, Halogenalkyl oder Aryl, das wahlweise halogensubstituiert ist,
mit der Maßgabe, dass mindestens einer der Substituenten R¹, R² oder R³ Wasserstoff bedeutet,
und
R⁴ eine Gruppe X-R⁵, wobei R⁵ eine Alkylgruppe oder eine Halogenalkylgruppe und X eine Bindung bedeuten; eine Gruppe der Formel -C(O)O(CH₂)_nY-, wobei n eine ganze Zahl von 1 bis 10 und Y eine Bindung oder eine Sulfonamidgruppe bedeuten; oder eine Gruppe -(O)_pR⁶(O)_q(CH₂)_t-, wobei R⁶ Aryl, das wahlweise halogensubstituiert ist, p 0 oder 1, q 0 oder 1 und t 0 oder eine ganze Zahl von 1 bis 10 bedeuten, mit der Maßgabe, dass t nicht 0 bedeutet, wenn q gleich 1 ist.Examples of monomeric organic compounds for use in the process of the invention are compounds of the formula (I),

in which mean:
R ¹ , R ² and R ³ independently represent a substituent selected from hydrogen, alkyl, haloalkyl or aryl which is optionally halogen-substituted,
with the proviso that at least one of the substituents R ¹ , R ² or R ^{3 is} hydrogen,
and
R ^{4 is} a group XR ⁵ , wherein R ^{5 is} an alkyl group or a haloalkyl group and X is a bond; a group of the formula -C (O) O (CH ₂ ) _n Y-, where n is an integer from 1 to 10 and Y is a bond or a sulfonamide group; or a group - (O) _p R ⁶ (O) _q (CH ₂ ) _t - wherein R ^{6 is} aryl which is optionally halogen-substituted, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that t does not mean 0 if q is equal to 1.

Suitable haloalkyl groups for R ¹ , R ² , R ³ and R ⁵ are fluoroalkyl groups. The alkyl groups may be straight-chain or branched and contain cyclic radicals.

For R ⁵ , the alkyl groups desirably contain 2 or more carbon atoms, suitably 2 to 20 carbon atoms and preferably 6 to 12 carbon atoms.

For R ¹ , R ² and R ³ , alkyl chains having 1 to 6 carbon atoms are generally preferred.

R ⁵ is preferably a haloalkyl group and more preferably a perhaloalkyl group, in particular a perfluoroalkyl group of the formula C _m F _{2m + 1} , in which m is an integer of 1 or more, favorably of 1-20 and preferably of 6-12, for example 8 or 10, means.

Suitable alkyl groups for R ¹ , R ² and R ³ have 1 to 6 carbon atoms.

However, it is preferred if at least one of the substituents R ¹ , R ² and R ^{3 is} hydrogen; Preferably, all substituents R ¹ , R ² and R ^{3 are} hydrogen.

When X is a group -C (O) O (CH ₂ ) _n Y-, n is an integer which gives a suitable spacer group. In particular, n is in the range of 1 to 5 and is preferably about 2.

Suitable sulfonamide groups for Y include the groups of the formula -N (R ⁷ ) SO ₂ ^- , wherein R ^{7 is} hydrogen or alkyl, such as C _1-4 alkyl, especially methyl or ethyl.

In one embodiment, the compound of the formula (I) is a compound of the formula (II) CH ₂ = CH-R ⁵ (II), wherein R ^{5 is} as defined above with reference to formula (I).

In Compounds of formula (II) X in formula (I) is a bond.

worin R⁷ wie oben definiert ist und insbesondere Wasserstoff darstellt und x eine ganze Zahl von 1 bis 9 ist, zum Beispiel eine ganze Zahl von 4 bis 9 und bevorzugt die Zahl 7. In diesem Fall handelt es sich bei der Verbindung der Formel (IV) um
1H,1H,2H,2H-Heptadecafluordecylacrylat.In a preferred embodiment, however, the compound of the formula (I) is an acrylate of the formula (III) CH ₂ = CR ⁷ C (O) O (CH ₂ ) _n R ⁵ (III), wherein n and R ^{5 are} as defined above in relation to formula (I) and R ^{7 is} hydrogen, C 1-10 -alkyl or C 1-10 -haloalkyl. R ⁷ is in particular hydrogen or C 1-6 -alkyl, such as methyl. A specific example of a compound of the formula (III) is a compound of the formula (IV)

wherein R ^{7 is} as defined above and in particular is hydrogen and x is an integer from 1 to 9, for example an integer from 4 to 9 and preferably the number 7. In this case, the compound of formula (IV ) around
1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate.

• (a) der Fleckfestigkeit gegen wässerige Flecken unter Verwendung eines Gemisches von Wasser und Isopropanol;
• (b) der Benetzungsfestigkeit des Textilerzeugnisses gegen Benetzung durch eine Reihe ausgewählter flüssiger Kohlenwasserstoffe unterschiedlicher Oberflächenspannung.

By using these compounds in the process of the invention, coatings with good levels of water repellency and oil repellency are achieved. These properties can be tested using the "3M Test Methods" such as the 3M Oil Repellency Test I (3M Test Methods Oct. 1, 1988) and a Water Repellency Test (3M Water Repellency Test II, Water / Alcohol Drop Test). 3M Test 1, 3M Test Methods, October 1, 1998). These tests are designed to detect a fluorochemical finish on all types of fabrics by measuring:

• (a) stain resistance to aqueous stains using a mixture of water and isopropanol;
• (b) the wetting resistance of the fabric against wetting by a series of selected liquid hydrocarbons of different surface tension.

These Tests should not serve as an absolute measure of the resistance of the fabric against Polluting by watery or oily Materials, since other factors, such as the structure of the Textile product, fiber type, dyes, other finishing agents, etc., which also influence stain resistance. However, these tests can be used to different Finish types together to compare. In the tests of water repellency are 3 drops of a standard test fluid, from given volume ratios of water and isopropanol, on the plasma-polymerized surface applied. The surface is considered this liquid viewed repellent, if after 10 seconds 2 of 3 drops the fabric do not wet. From this, the measure of water repellency is the test liquid with the larger share of isopropanol which passes the test. In the case of the test of oil repellency 3 drops of hydrocarbon liquid on the coated surface applied. If after 30 seconds no penetration or wetting of the fabric at the interface between liquid and fabric occurs and no wicking by 2 out of 3 drops is visible, the test is passed.

to Evaluation of oil repellency is the test fluid with the highest Number taken from the surface of the fabric not wetted (with an increasing number of a decreasing hydrocarbon chain and decreasing surface tension corresponds).

The results obtained using these tests are dependent of the type of substrate variable, in particular of the roughness of the substrate, however, certain products obtained using obtained in the process of the invention, water repellency values of up to 10 and oil resistance from 8 at large-scale Production. In fact, some coated materials showed repellency Heptane and pentane, which represents a degree of oil resistance, the outside the normal 3M scale is.

Further Compounds of formula (I) are styrene derivatives useful in the art the polymerization are well known.

suitable Plasmas for use in the process of the invention include imbalance plasmas, such as such as the plasmas caused by radio frequency (RF), microwaves or DC (DC) can be generated. They can be at atmospheric pressure or printing under atmospheric pressure operated as known in the art. you will be however, especially generated by radio frequency (RF).

The gas introduced into the plasma chamber can only consist of a vapor of the monomeric compound consist solely of however, it is preferably combined with a carrier gas, in particular an inert gas such as helium or argon. Helium, in particular, is a preferred carrier gas because it minimizes fragmentation of the monomer.

The ratio of monomer gas to carrier gas is favorably in the range of 100: 1 to 1: 100, for example in the range of 10: 1 to 1: 100, and in particular in the range of 1: 1 to 1:10, for example at about 1 : 5th This helps to achieve the high throughputs required in the process of the invention. The gas or gas mixture is conveniently introduced at a rate of at least 1 standard cubic centimeter (Ncm ³ ) per minute, and preferably at a flow rate in the range of 1 to 100 Ncm ³ .

The Gases are conveniently due to a reduced pressure inside the chamber due to a Vacuum pump sucked into the chamber; but you can also go to the chamber be pumped into it.

The Polymerization is conveniently using vapors of compounds of formula (I) in the chamber made on Printing in the range of 0.01 to 300 mbar and desirably to about 80 to 100 mbar are kept.

By Applying a high-frequency voltage, for example at a frequency of 13.56 MHz, a glow discharge is then fired. This will be convenient using electrodes applied inside or outside located in the chamber; however, they are in the case of larger chambers preferably provided inside.

The applied fields suitably match a power of up to 500W, suitably about 40W as a pulsed field. The pulses are created in a sequence, which results in very low average performances, for example in one Sequence in which the ratio of duty cycle: Off duration in the range of 1: 500 to 1: 1000 lies. Special examples for such a sequence are sequences in which the power is turned on for 20 μs and while 1 000 to 20 000 μs is off. Typical mean performances that way be achieved are 0.04 W.

The Fields are conveniently Applied for 30 seconds to 90 minutes, preferably 5 to 60 minutes, in dependence on the kind of the compound of the formula (I) and the substrate, etc.

It it was found that the plasma polymerization of compounds of formula (I), in particular at medium powers, which are significant are lower than they used to be were applied for the deposition of highly fluorinated coatings leads, the high values of water repellency and oil repellency, even if she in a big one scale are generated. additionally there is a structural retention of the compound of formula (I) high level in the coating layer, which is the direct polymerization of the alkene monomer, for example, a fluoroalkenic monomer, via its highly sensitive Double bond can be attributed.

It has been found, especially in the case of the polymerization of Compounds of the above formula (III) that the plasma polymerization with a plasma of low power results in well-adherent coatings that show excellent water and oil repellency. The coatings are also of good uniformity Thickness.

The higher Level of structural retention may be due to free-radical polymerization, the while the shutdown phase occurs, and the lower fragmentation during the Switching be assigned.

The Gas is conveniently over a Temperature gradient passed to the chamber. The gas is for example via a heated pipe pumped, which leads from a gas supply to the plasma chamber. The Conduit is suitably heated so that the temperature of the into the chamber entering gas is 30 to 60 ° C, depending on the type of used Monomer. The temperature of the gas entering the chamber is especially higher, preferably about 10 ° C higher than the gas that leaves the gas supply. The gas supply will suitably at ambient temperature or at a slightly elevated temperature such as about 30 ° C which in turn depends on the type of monomer involved.

Applicants have found that by applying the heating of the gas supply lines and the chamber in this way, the monomer vapor is effectively transported into the chamber and, when in the chamber, remains movable. This leads to efficient separation and polymerization of the monomer and minimizes gas condensation that occurs at "cold spots" of the monomer Pipe system could occur. Although heating the chamber in plasma etching processes has previously been used to keep the etch products mobile so that they can be pumped out of the chamber, such a process is not required in the present case, so heating is preferred.

New devices for use in the method described above form a further aspect of the invention. In particular, the invention includes a plasma deposition chamber, a pumping system configured to deliver monomer in gaseous form into the chamber, at least two electrodes configured to fire a plasma inside the chamber, and a power controller which is programmed to pulse the power delivered to the electrodes in such a way as to produce a plasma at a power of 0.001 to 500 W / m ³ within a plasma zone inside the chamber.

The Pumping system is conveniently a system that big Quantities of vapors can deliver to the chamber and make sure that this amount for the minimum residence time remains in the chamber to achieve the desired Effect is required. It can be a set of pumps and lines having high conductance. The pumping system can also be designed in this way be that it evacuates gas from the chamber as needed, to pump out air and / or reduce pressure.

at a particular embodiment the pumping system has two pumps. A first pump or Roots pump, favorably a pump with high capacity, serves to pump out vapors including Water vapor or other contaminants from the chamber. Around to do so effectively and within a reasonable time frame the size of the chamber carry out to be able to the pump is conveniently near arranged with the chamber and with a single straight line with greatest possible Diameter associated with it. In the line a valve is provided, the can be closed when the chamber was pumped out.

A second pump is conveniently a low volume flow pump, such as a dry one Rotary vane pump. This is suitably through the same opening as the first pump is connected to the chamber. She is so educated that they include monomer, along with any carrier gas promote suitable throughput into the chamber and the desired Pressure and the desired Residence of the gas in the chamber can be maintained.

The outlets the pumping device are conveniently connected to a furnace, where about any remaining monomer or fragments be burned off before the gases release safely into the atmosphere can be.

The Device also advantageously has a heating device for the chamber on. This heater can be integrated with the walls of a chamber be present or in a housing surrounding the chamber. She can electric Elements or circulating heated, oil-filled elements, conveniently under the control of a temperature control device to ensure that the desired temperature is maintained within the chamber.

The Device preferably further comprises a container for monomer, the by a suitable line and valve assembly with the chamber connected is. This container is preferably equipped with a heater which makes it possible to if necessary, the monomer to a temperature above the To warm ambient temperature, before it was introduced to the chamber becomes. Preferably, the container, the pipe leading from him to the chamber, and the chamber itself heated, and the heater is designed so that an increasing Temperature gradient along the path of the monomer is generated.

A Supply for carrier gas may, if necessary, be connected to the container, and gas if necessary, this supply can be introduced into the container to allow sufficient gas flow into the chamber generate the desired Result.

at the practical implementation become the objects to be coated in a batchwise procedure introduced into the chamber. In a particular embodiment these are ready-to-wear garments onto which a water and / or oil repellent Apply coating is. By deposition of the polymer on the finished garment instead of deposition on the one used in the manufacture Fabric can be achieved an all-round coating, including Areas of zippers, snaps or seams, which otherwise remained uncoated.

The Chamber is subsequently evacuated, for example, using the entire pump sequence, however, in particular using the large Roots pumps, if provided are.

If The chamber is evacuated, is monomer vapor, which favorably heated will, out of the container entered the chamber. This is done, for example, that the monomer vapor using a second pump from a Container, in which a supply of liquid Monomer is submitted, is subtracted. This container will favorably heated to a temperature sufficient to cause evaporation of the monomer.

Prefers are also the pipes and lines that lead from the container to the chamber, heated. This means that it is possible is to ensure that no monomer by condensation in the Supply lines is lost.

if necessary can be a carrier gas, which may be an inert gas such as argon or helium, and preferably Helium, are passed through the chamber to achieve a gas flow which is sufficient to the desired Concentrations and the volume-related homogeneity of the monomer to achieve in the chamber.

alternative can monomer vapor from the container deducted and then mixed with the carrier gas become. Preference is given to the monomer vapor before mixing by a Device for controlling the liquid / vapor throughput passed. This arrangement allows a controllable Mix to achieve the desired ratio of carrier gas: monomer. In addition, can the environment of the monomer and in particular the temperature independent of the flow requirements to be controlled. Furthermore, can reactive monomers conveniently under an inert atmosphere, for example, a nitrogen atmosphere, stored in the container. Of the container can suitably be pressurized so that the nitrogen pressure above the atmospheric pressure so as to reduce the flow of monomer vapor out of the container to assist the chamber, which is at a lower pressure.

Subsequently, will within the chamber ignited a glow discharge, for example by applying a voltage, such as a high frequency voltage, for example at 13.56 MHz. Then the power is pulsed as described above, to produce an average low power. As a result, will activated a monomer and bound to the surface of the substrate, whereupon it builds a polymer layer. In the process of the Invention applied lower powers form unsaturated monomers even layers high structural integrity. The relevant Effect depends Depending on the type of monomer used, however, the specified above excellent water repellency and / or oil repellency result.

The Invention will be described below by way of example with reference to the attached schematic drawings closer explains; show it:

1 a schematic representation of a Monomerzuführsystems that can be used in an embodiment of the invention use;

2 a schematic representation of a pumping system that can be used in an embodiment of the invention, and

3 a schematic representation of an alternative device that can be used in an embodiment of the invention.

In the 1 The device shown is a process system that contains a plasma chamber ( 1 ) contains. Heating elements that are filled with circulating heated oil are in the outer walls of the plasma chamber ( 1 ) built-in. The temperature within the chamber is measurable by a thermocouple (not shown) and this information is used to control the heating so that the required temperature within the plasma chamber (FIG. 1 ) can be maintained. Furthermore, two opposing electrodes are provided within the plasma chamber, between which a plasma zone of approximately 1 m ^{3 is} specified. The electrodes are connected to a suitable power supply that is controllable and programmable.

A monomer feed line ( 3 ), which is a valve ( 5 ), serves for feeding into the plasma chamber ( 1 ). At the end of the line ( 3 ) is a lockable chamber ( 7 ) for monomer. Within the Kam mer ( 7 ) is a carrier ( 9 ), on which an open container ( 11 ) for monomer ( 13 ) can be used. The chamber ( 7 ) is provided with a controllable heater, for example a heating tape ( 15 ), which is around the chamber ( 7 ) extends around.

In addition, a source of inert gas ( 17 ), such as for argon or helium, with the chamber ( 7 ) via a line ( 19 ), in which a valve ( 21 ) and a manually operated valve ( 23 ) together with a mass flow controller ( 25 ) are provided. The gas supply is adjustable and can be adjusted by means of an indicator ( 27 ) to be watched.

The plasma chamber ( 1 ) is equipped with a pump assembly which in 2 is illustrated schematically. It comprises a combination of a Roots pump with a rotary vane pump, which serves to evacuate the chamber. A Roots pump ( 29 ) is via a line ( 31 ), which is preferably straight and has the largest possible diameter, connected to the plasma chamber. In this case, the diameter of the pipe is 160 mm. By ensuring that in the line ( 31 ) there are no bends, the loss of conductivity can be minimized. A separating valve ( 33 ) is in the lead ( 31 ) provided to the pump ( 29 ) to be separated from the plasma chamber.

Furthermore, a rotary vane pump ( 35 ) with a small volumetric flow rate, which downstream of the valve ( 33 ) over a smaller line ( 37 ), for example, 63 mm in diameter, with an automatic pressure control valve (APC valve) ( 39 ) and a separating valve ( 41 ), with the line ( 31 ) is connectable. A flexible bypass line ( 43 ), further equipped with a valve ( 45 ), the Roots pump connects ( 29 ) directly with the rotary vane pump ( 35 ).

Finally, a stove ( 47 ) downstream of the rotary vane pump ( 35 ), which serves to burn gases that are withdrawn from the system.

The illustrated combination of Roots pump and rotary vane pump results in a total pumping speed of the order of 350 m ³ / h, which allows a rapid pumping out of the plasma chamber.

An alternative arrangement is in 3 shown. In this illustration, the electrodes ( 2 ) within the chamber ( 1 ). These are via an RF tuning unit ( 6 ) electrically with an HF generator ( 4 ) connected. The HF generator ( 4 ) is determined by a function generator ( 8th ), which is set to generate pulses in the RF range, as described above. The RF tuner ensures that the pulsation within the chamber ( 1 ) to the pulse generation in the generator ( 4 ) is aligned.

In the present example, the pumping system is slightly different, since the Roots pump ( 29 ) and the rotary vane pump ( 35 ) via a single three-way valve ( 40 ), between which process and coarse pumps can be selected, the three-way valve being the valves ( 41 ) and ( 45 ) of the embodiment of 2 replaced. The administration ( 37 ), the control valve ( 39 ) for the process pressure is also connected to this valve. As a result, the combination of Roots pump and rotary vane pump can be used to move gases through the process chamber (FIG. 1 ) and draw them in a roughly similar manner as with reference to the 1 and 2 described as vent gas to the furnace ( 47 ). The rapid pumping of gas from inside the chamber can be achieved by opening the valves ( 33 ) and ( 40 ) and operating the pump ( 29 ) and, if necessary, also the pump ( 35 ) be performed. The Roots pump ( 29 ) can be closed by closing the valve ( 33 ) and adjusting the valve ( 40 ) and a more controlled gas flow through the chamber can be achieved by using the pump ( 35 ), the gas through the line ( 37 ), when the valve ( 39 ) is open.

In this device, the arrangement for supplying monomer is modified to make it more controllable. In detail, a separate monomer handling unit ( 10 ) intended. It has a monomer reservoir ( 12 ), in which monomer can be kept under controlled environmental conditions. The monomer may be, for example, in the dark under an atmosphere of inert gas such as nitrogen supplied by a suitable gas supply ( 14 ). These conditions minimize the risk of the monomer polymerizing prematurely.

The monomer can be passed over a line ( 16 ) from the reservoir ( 12 ) derived from the monomer tank ( 11 ) (not shown in this example) down. This gas flow can thereby supported, that the pressure of the inert gas within the reservoir is maintained at a pressure slightly above atmospheric pressure, so as to generate a pressure difference. The system further includes a nitrogen blow-off valve ( 32 ) intended.

The administration ( 16 ) suitably introduces monomer into a liquid / vapor throughput regulator ( 18 ) in a temperature-controlled gas unit ( 20 ) is included. The temperature within the controller ( 18 ) is monitored and controlled to ensure that condensed monomer is vaporized; the steam with the required concentration leaves the regulator via a valve ( 22 ), where it enters a gas injector unit ( 24 ) entry.

Within this unit, the monomer vapor is mixed with the requisite amount of carrier gas, such as helium, coming from a suitable supply ( 17 ) via a mass flow controller ( 26 ) for helium in the injector unit ( 24 ) is initiated. Valves ( 28 . 30 ) can be used to separate the helium supply ( 17 ), if necessary. The temperature of the controller ( 26 ) can be independently controlled so that gas is injected into the injector unit at the pressure suitable for obtaining the desired mixture ( 24 ) is introduced. The in the injector unit ( 24 ) are mixed via a line ( 3 ) passing through a valve ( 5 ) is shut off in a similar way in the chamber ( 1 ), as in relation to 1 has been described.

example 1

A pillow cover was placed inside a plasma chamber of the device of 1 and 2 suspended between the electrodes and thus within the plasma zone. Further, a sample of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (10 g) was added to the container ( 11 ) within the monomer chamber ( 7 ) brought. At this time, the valves are 5 . 21 . 23 and 33 closed.

The plasma chamber was then opened by opening the valves 33 and 45 and putting the pumps into operation 29 . 35 to evacuate the air from the chamber rapidly (within 5 minutes) to a pressure of 2 × 10 ^-3 bar. The rotary vane pump 35 was then closed by closing the valves 33 and 45 disconnected from the system.

The plasma chamber was then passed through the heater in the walls of the process chamber ( 1 ), and maintaining a temperature of 40-50 ° C, and more preferably 50 ° C.

Similarly, the heating tape 15 turned on to the monomer chamber 7 to a temperature of 45 ° C and keep it at this temperature.

Then the valves became 39 and 41 open and also the valves 21 and 23 , and helium gas from the supply ( 17 ) was made by putting the rotary vane pump into operation 35 with a flow rate of 60 Ncm ³ into the chamber ( 7 ) drawn. When passing over the monomer, the helium gas acted as a carrier for entraining monomer vapor into the plasma chamber.

To a period of 2 minutes while whose remaining air was removed from the system, became the desired Pressure within the chamber is reached, and an RF plasma was placed between the Electrodes ignited. The power supply was pulsed to turn on the power for 20 μs and while 20,000 μs was off.

The gases drawn through the plasma chamber were passed over the line 37 and the pump 35 pumped out and in the oven 47 promoted, which was kept at 300 ° C.

After 30 minutes the valves became 39 and 41 closed to the pump 35 and the system was vented with dry nitrogen. The cushion cover was removed and oil repellency and repellency tested using the 3M Oil Repellency Test I (3M Test Methods Oct. 1, 1988) and water repellency test (3M Water Repellency Test II, Water / Alcohol Drop Test , 3M Test 1, 3M Test Methods, October 1, 1998). Even after washing in a conventional washing machine, the results were 10 for water repellency and 8 for oil repellency.

in the In contrast, a pillow cover, under the same conditions, but with 200 W RF power at 13.56 MHz was treated with continuous application, a coating, which was easy to rub off.

Claims (20)

A method of depositing a polymeric material on a substrate, the method comprising: introducing a monomeric material in a gaseous state into a plasma deposition chamber in which a plasma zone has a volume of at least 0.5 m ³ , igniting a glow discharge inside the chamber and applying a plasma Voltage in the form of a pulsed field at a power of 0.001 to 500 W / m ³ for a time sufficient to form a polymer layer on the surface of the substrate. The method of claim 1, wherein the plasma zone has a volume of about 1 m ³ or more inside the chamber. The method of claim 2, wherein the plasma zone has a volume of 1 to 10 m ³ . Method according to one of claims 1 to 3, wherein a power of 0.001 to 100 W / m ^{3 is} applied. The method of claim 4, wherein a power of 0.04 to 100 W / m ^{3 is} applied. Method according to one of the preceding claims, in the monomer material is an unsaturated organic compound which has a chain of carbon atoms optionally are substituted with halogen. A method according to claim 6 wherein the monomeric material is a compound of formula (I)

wherein R ¹ , R ² and R ³ independently represent a substituent selected from hydrogen, alkyl, haloalkyl or aryl which is optionally halogen-substituted, with the proviso that at least one of the substituents R ¹ , R ² or R ³ Is hydrogen, and R ^{4 is} a group XR ⁵ , wherein R ^{5 is} an alkyl group or a haloalkyl group and X is a bond; a group of the formula -C (O) O (CH ₂ ) _n Y-, where n is an integer from 1 to 10 and Y is a bond or a sulfonamide group; or a group - (O) _p R ⁶ (O) _q (CH ₂ ) _t - wherein R ^{6 is} aryl which is optionally halogen-substituted, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that t does not mean 0 if q is equal to 1. Process according to Claim 7, in which the compound of the formula (I) is an acrylate of the formula (III) CH ₂ = CR ⁷ C (O) O (CH ₂ ) _n R ⁵ (III) wherein n and R ^{5 are} as defined above in claim 7 and R ^{7 is} hydrogen or C _1-6 alkyl. A method according to claim 8, wherein the acrylate is the Formula (III) is 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate. Method according to one of the preceding claims, in the monomer compound in a gaseous state in combination with a carrier gas introduced into the chamber becomes. The method of claim 10, wherein the carrier gas is helium is. A method according to any one of the preceding claims, wherein the gaseous material is introduced into the chamber at a rate of at least 1 standard cubic centimeter (Ncm ³ ) per minute. Method according to one of the preceding claims, in the vapors of compounds of the formula (I) at pressures of 0.01 to 300 mbar be maintained in the chamber. Method according to one of the preceding claims, in the power is pulsed in a sequence at which the power while 20 μs switched on and while 1000 to 20000 μs is off. Method according to one of the preceding claims, in along the gas a temperature gradient is introduced into the chamber. Method according to one of the preceding claims, in the chamber during the deposition process is heated. Apparatus for depositing a polymeric material on a substrate comprising: a plasma deposition chamber, at least two electrodes selected to fire a plasma inside the chamber, a pumping system capable of delivering monomer gas into the chamber, and a power controller; which is programmed to pulse the power delivered to the electrodes so as to produce a plasma at a power of 0.001 to 500 W / m ³ within a plasma zone inside the chamber, the plasma zone having a volume of at least 0 , 5 m ³ . Apparatus according to claim 17, further comprising a heater for the Chamber has. Apparatus according to claim 17 or 18, further a container for monomer having, which is connected to the chamber. Apparatus according to claim 19, wherein a heating means is designed so that an increasing temperature gradient between the container and the chamber is generated.